A fuel cell system includes: a first fuel cell including a first anode and a first cathode, wherein the first anode is configured to output a first anode exhaust gas; a first oxidizer configured to receive the first anode exhaust gas and air from a first air supply, to react the first anode exhaust gas and the air in a preferential oxidation reaction, and to output an oxidized gas; a second fuel cell configured to act as an electrochemical hydrogen separator, the second fuel cell including: a second anode configured to receive the oxidized gas from the first oxidizer and to output a second anode exhaust gas, and a second cathode configured to output a hydrogen stream; and a condenser configured to receive the second anode exhaust gas and to separate water and CO2.
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7. A method of processing fuel cell exhaust, the method comprising:
at a first oxidizer, receiving a first anode exhaust gas from a first anode of a first fuel cell and air from a first air supply, wherein the first fuel cell comprises a first cathode;
outputting an oxidized gas from the first oxidizer;
at a second fuel cell having a second anode and a second cathode, receiving the oxidized gas at the second anode, electrochemically separating hydrogen in the oxidized gas, outputting a hydrogen stream from the second cathode, and outputting a second anode exhaust gas from the second anode.
1. A fuel cell system comprising:
a first fuel cell comprising a first anode and a first cathode, wherein the first anode is configured to output a first anode exhaust gas;
a first oxidizer configured to receive the first anode exhaust gas and air from a first air supply, to react the first anode exhaust gas and the air in a preferential oxidation reaction, and to output an oxidized gas;
a second fuel cell configured to act as an electrochemical hydrogen separator, the second fuel cell comprising:
a second anode configured to receive the oxidized gas from the first oxidizer and to output a second anode exhaust gas, and
a second cathode configured to output a hydrogen stream; and
a condenser configured to receive the second anode exhaust gas and to separate water and CO2.
2. The fuel cell system of
3. The fuel cell system of
4. The fuel cell system of
5. The fuel cell system of
6. The fuel cell system of
a first heat exchanger configured to receive and cool the first anode exhaust gas and output a first partially-cooled gas;
a first CO shift reactor configured to receive the first partially-cooled gas, to perform a first CO shift reaction at a first temperature on the first partially-cooled gas, and to output a first shifted gas;
a second heat exchanger configured to receive and cool the first shifted gas, and to output a second partially-cooled gas;
a second CO shift reactor configured to receive the second partially-cooled gas, to perform a second CO shift reaction at a second temperature on the second partially-cooled gas, and to output a second shifted gas; and
a third heat exchanger configured to receive and cool the second shifted gas, and to output a cooled gas;
wherein the first anode exhaust gas received at the first oxidizer is the cooled gas output from the third heat exchanger; and
wherein the first temperature is higher than the second temperature.
8. The method of
at a condenser, receiving the second anode exhaust gas and separating water and CO2 in the second anode exhaust gas; and
at a compressor, receiving the CO2 from the condenser and outputting liquefied CO2.
9. The method of
at a first heat exchanger, cooling the first anode exhaust gas and outputting a first partially-cooled gas;
at a first CO shift reactor, performing a first CO shift reaction at a first temperature on the first partially-cooled gas and outputting a first shifted gas;
at a second heat exchanger, cooling the first shifted gas and outputting a second partially-cooled gas;
at a second CO shift reactor, performing a second CO shift reaction at a second temperature on the second partially-cooled gas and outputting a second shifted gas; and
at a third heat exchanger, cooling the second shifted gas and outputting a cooled gas;
wherein the first anode exhaust gas received at the first oxidizer is the cooled gas output from the third heat exchanger; and
wherein the first temperature is higher than the second temperature.
10. The method of
11. The method of
at a second oxidizer, receiving a first portion of the hydrogen stream and air from a second air supply and outputting an oxidized hydrogen stream; and
transferring heat from the oxidized hydrogen stream to a cathode inlet stream received by the first cathode.
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This application is a divisional of U.S. patent application Ser. No. 16/095,261 filed on Oct. 19, 2018, which is a U.S. National Phase application under 35 U.S.C. § 371 of International Application No. PCT/US2017/028594, filed on Apr. 20, 2017, which claims the benefit of U.S. Provisional Patent Application No. 62/325,711, filed on Apr. 21, 2016, which are hereby incorporated by reference in their entireties.
The present disclosure relates to carbon dioxide (CO2) separation in direct molten carbonate fuel cells (“DFC”). In particular, the present disclosure relates to an electrochemical hydrogen separator (“EHS”) receiving a CO2-rich anode exhaust stream from a DFC and concentrating the CO2 for sequestration.
In a CO2 separation system for a DFC, the CO2-rich anode exhaust stream also contains water vapor and unused fuel, including mostly hydrogen and carbon monoxide (CO). To make the stream ready for CO2 capture (i.e., separation) for sequestration or use, some processing or post-treatment is required.
In certain embodiments, a fuel cell system includes a first fuel cell having a first anode and a first cathode, wherein the first anode is configured to output a first anode exhaust gas. The system further includes a first oxidizer configured to receive the first anode exhaust gas and air from a first air supply, to react the first anode exhaust gas and the air in a preferential oxidation reaction, and to output an oxidized gas. The system further includes a second fuel cell configured to act as an electrochemical hydrogen separator (“EHS”). The second fuel cell includes a second anode configured to receive the oxidized gas from the first oxidizer and to output a second anode exhaust gas, and a second cathode configured to output a hydrogen stream. The system further includes a condenser configured to receive the second anode exhaust gas and to separate water and CO2.
In other embodiments, a method of processing fuel cell exhaust includes, at a first oxidizer, receiving a first anode exhaust gas from a first anode of a first fuel cell and air from a first air supply, and outputting an oxidized gas from the first oxidizer. The method further includes, at a second fuel cell having a second anode and a second cathode, receiving the oxidized gas at the second anode, electrochemically separating hydrogen in the oxidized gas, outputting a hydrogen stream from the second cathode, and outputting a second anode exhaust gas from the second anode.
In other embodiments, a fuel cell system includes a fuel cell having an anode and a cathode, wherein the anode is configured to output an anode exhaust gas. The system further includes a condenser configured to receive and condense the anode exhaust gas, to separate water from the anode exhaust gas to form a dried anode exhaust gas, and to separately output the water and the dried anode exhaust gas. The system further includes a pressure swing adsorption unit configured to receive the dried anode exhaust gas, and to output a hydrogen stream and a separate CO2 stream.
In other embodiments, a method of processing fuel cell exhaust includes, at a condenser, receiving anode exhaust gas from an anode of a fuel cell, outputting a dried anode exhaust gas stream, and separately outputting a water stream. The method further includes, at a first compressor, compressing the dried anode exhaust gas stream and outputting a compressed anode exhaust gas stream. The method further includes, at a pressure swing adsorption (“PSA”) unit, receiving the compressed anode exhaust gas stream, outputting a hydrogen stream, and separately outputting a CO2 stream.
These and other advantageous features will become apparent to those reviewing the disclosure and drawings.
Referring generally to the figures, disclosed herein is a fuel cell subsystem for post-processing fuel cell anode exhaust gas to provide CO2 sequestration.
Conventionally, combustibles in an anode exhaust gas may be reacted in an oxidizer. Oxygen rather than air is supplied to the oxidizer because nitrogen present in air may dilute the CO2 in the anode exhaust gas. An air separation subsystem must be incorporated to provide the necessary oxygen to the oxidizer. However, when using oxygen, water is injected as a coolant in the oxidizer to maintain the oxidizer at a desired temperature level (e.g., to avoid overheating a catalyst). The oxidizer generates an oxidizer exhaust including at least water and CO2. Heat generated in the oxidizer is then used to preheat a cathode inlet stream. After recuperative heat exchange, the anode exhaust/oxidizer exhaust stream is cooled down in a condenser to remove water. A condenser downstream from the oxidizer separates and removes the injected water and any other water present in the exhaust stream, generating oxidizer exhaust with a higher concentration of CO2 ready for sequestration. In one example, when feeding oxygen to an oxidizer in a fuel cell system using greenhouse gas (“GHG”) from a pulverized coal (“PC”) boiler steam cycle power plant, the CO2 stream for sequestration contains approximately 89% CO2 and 10% water, with 74% fuel utilization. When air is fed to the oxidizer rather than oxygen, the CO2 content is reduced to approximately 58%.
Referring to
A fuel cell system 1 includes a first fuel cell 10 having a cathode 12 (i.e., a first cathode) and an anode 14 (i.e., a first anode). According to an exemplary embodiment, the first fuel cell 10 may be a DFC. The anode 14 outputs an anode exhaust gas, including at least CO2, hydrogen, water, and CO. A first heat exchanger 20 receives the anode exhaust gas from the DFC and partially cools the anode exhaust gas. The first heat exchanger 20 then outputs a first partially-cooled gas. The first partially-cooled gas is transformed through a high-temperature (“HT”) CO shift reaction (e.g., water-gas shift reaction) in a first shift reactor 21, forming a first shifted gas, which is received by a second heat exchanger 22. The first shift reactor 21 is configured to operate at a first temperature in a range of approximately 310° C. to 450° C. The first shift reactor 21 may be configured to shift CO and water into CO2 and hydrogen, such that the first shifted gas has a higher concentration of CO2 and hydrogen than the first partially-cooled gas. The second heat exchanger 22 partially cools the first shifted gas and outputs a second partially-cooled gas. The second partially-cooled gas is transformed through a low-temperature (“LT”) CO shift reaction in a second shift reactor 23, forming a second shifted gas, which is received by a third heat exchanger 24. The second shift reactor 23 is configured to operate at a second temperature in a range of approximately 200° C. to 250° C., such that the first temperature is higher than the second temperature. The second shift reactor 23 may be configured to shift CO and water into CO2 and hydrogen, such that the second shifted gas has a higher concentration of CO2 and hydrogen than the second partially-cooled gas. The third heat exchanger 24 cools the second shifted gas to a desired temperature and outputs a cooled gas. According to an exemplary embodiment, the temperature of the cooled gas is based on a range of temperatures acceptable by an oxidizer 30 downstream from the third heat exchanger 24.
The cooled gas is mixed with air, rather than oxygen, which is provided (i.e., injected) by an air supply 26 (i.e., first air supply, controlled air supply, etc.), forming a mixed gas. According to an exemplary embodiment, the air supply 26 may be controlled to establish a preferred ratio of air to any one of CO2, hydrogen, water, and/or CO making up the cooled gas. This preferred ratio may be based on the requirements of the oxidizer. The mixed gas is then fed to the oxidizer 30, which is configured to perform a preferential oxidation reaction for conversion of CO to CO2. Preferential oxidation is a chemical process for removing CO. This process uses a low-temperature shift reactor (e.g., similar to the second shift reactor 23) followed by a staged preferential oxidizer for oxidizing CO using oxygen in the presence of a noble metal catalyst (e.g., platinum, palladium-cobalt, palladium-copper, gold, etc.). The oxidizer 30 outputs an oxidized gas containing CO2 for sequestration and generates heat due to the reaction. A fourth heat exchanger 32 receives the oxidized gas from the oxidizer 30 and cools the oxidized gas, forming, at least in part, an anode inlet stream 34. According to an exemplary embodiment, the oxidizer 30 generates exhaust, separate from the oxidized gas containing CO2. Because exhaust from the oxidizer 30 does not form part of the oxidized gas output, air may be used for the oxidizer, eliminating the need for an air separation unit and/or water injection (e.g., for oxidizer temperature control).
As shown in
The anode 44 of the EHS 40 generates a second anode exhaust gas. The second anode exhaust gas may be fed to a condenser 60, which separates the second anode exhaust gas into a CO2 stream 61 and a water stream (i.e., condensate) 66. The CO2 stream 61 from the condenser 60 is then fed through a CO2 compressor 62 to liquefy at least a portion of the CO2 stream 61, generating a highly concentrated CO2 supply 64 suitable for sequestration and/or export (i.e., transportation) to a point of use (e.g., for food processing). According to an exemplary embodiment, after removal of water in the condenser 60 to the water stream 66, the CO2 stream 61 includes approximately 89% CO2 and approximately 9% water.
As shown in
In the embodiment shown in
Referring now to
A fuel cell system 100 includes a fuel cell 110 having a cathode 112 and an anode 114. According to an exemplary embodiment, the fuel cell 110 may be a DFC substantially same as the first fuel cell 10. The anode 114 outputs an anode exhaust gas, including at least CO2, hydrogen, water, and CO. A first heat exchanger 120 receives the anode exhaust gas from the DFC and partially cools the anode exhaust gas. The first heat exchanger 120 outputs a first partially-cooled gas. The first partially-cooled gas is transformed through a high-temperature CO shift reaction in a first shift reactor 121, forming a first shifted gas, which is received by a second heat exchanger 122. The first shift reactor 121 is configured to operate at a first temperature in a range of approximately 310° C. to 450° C. The first shift reactor 121 may be configured to shift CO and water into CO2 and hydrogen, such that the first shifted gas has a higher concentration of CO2 and hydrogen than the first partially-cooled gas. The second heat exchanger 122 partially cools the first shifted gas and outputs a second partially-cooled gas. The second partially-cooled gas is transformed through a low-temperature CO shift reaction in a second shift reactor 123, forming a second shifted gas, which is received by a condenser 160. The second shift reactor 123 is configured to operate at a second temperature in a range of approximately 200° C. to 250° C., such that the first temperature is higher than the second temperature. The second shift reactor 123 may be configured to shift CO and water into CO2 and hydrogen, such that the second shifted gas has a higher concentration of CO2 and hydrogen than the second partially-cooled gas. The condenser 160 separates the second shifted gas into a dried (e.g., dehydrated) anode exhaust gas stream 161, containing at least CO2 and hydrogen, and a separate water stream (i.e., condensate) 166. For example, substantially all of the water is removed from the anode exhaust gas stream when forming the dried anode exhaust gas stream 161. The dried anode exhaust gas stream 161 from the condenser 160 is then fed through a compressor 162, forming a compressed anode exhaust gas stream, which is then fed through a third heat exchanger 163, to further cool the compressed anode exhaust gas stream. According to another exemplary embodiment, the third heat exchanger 163 may be disposed upstream from the compressor 162 (e.g., between the condenser 160 and the compressor 162) and is configured to cool the dried anode exhaust gas stream 161.
The system 100 includes a pressure swing adsorption (“PSA”) unit 170. The PSA unit 170 is configured to receive the compressed anode exhaust gas stream from the third heat exchanger 163 and separate the stream into a hydrogen stream 150 and a CO2 stream 165. In the PSA unit 170, the gases other than hydrogen (e.g. mostly CO2 and some water) are adsorbed by an adsorbent bed media at high pressures and a pure hydrogen stream 150 is outputted from the PSA unit 170 at a pressure close to (e.g., substantially the same as) an inlet pressure of the compressed anode exhaust gas stream received at the PSA unit 170. The hydrogen stream 150 is generated as co-product and may be used in the system 100 or exported. After the adsorbent bed media in the PSA unit 170 reaches its maximum adsorbent capacity, it is purged to remove the adsorbed gases, which generate the CO2 stream 165. This purging occurs by de-sorption, accomplished by lowering the pressure to near atmospheric pressure of approximately 20 psia. The CO2 stream 165 is then fed to a CO2 compressor 167 to liquefy at least a portion of the CO2 stream 165, generating a sequestered CO2 supply 164.
According to an exemplary embodiment, the system 100 may transform a portion of the hydrogen stream 150 in the same way as the hydrogen stream 50 as shown in
With regard to either system 1, 100, according to another exemplary embodiment, a process for sequestering CO2 may include consuming all hydrogen and other combustibles in an oxidizer and utilizing the energy content for preheating a cathode inlet stream.
In certain embodiments, a fuel cell system includes a fuel cell having an anode and a cathode, an oxidizer, and an electrochemical hydrogen separator. The oxidizer is configured to receive anode exhaust gas from the anode and air from a controlled air supply and react the anode exhaust gas and the air in a preferential oxidation reaction. The separator is configured to receive oxidized gas from the oxidizer and to form separate streams of hydrogen and CO2 from the remaining gas. A condenser is configured to receive the CO2 stream from the oxidizer and condense the stream to separate water and liquefy CO2.
In other embodiments, a fuel cell system includes a fuel cell having an anode and a cathode, a condenser, and a pressure swing adsorption unit. The condenser is configured to receive and condense anode exhaust gas from the anode and separate a water stream from the remaining condensed gas. A compressor receives and compresses the remaining condensed gas and feeds compressed gas to the pressure swing adsorption unit. The pressure swing adsorption unit separates a hydrogen stream and a CO2 stream. The CO2 stream is received by a second compressor configured to liquefy CO2.
As utilized herein, the terms “approximately,” “about,” “substantially”, and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numerical ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and claimed are considered to be within the scope of the invention as recited in the appended claims.
The terms “coupled,” “connected,” and the like as used herein mean the joining of two members directly or indirectly to one another. Such joining may be stationary (e.g., permanent) or moveable (e.g., removable or releasable). Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate members being attached to one another.
References herein to the positions of elements (e.g., “top,” “bottom,” “above,” “below,” etc.) are merely used to describe the orientation of various elements in the Figures. It should be noted that the orientation of various elements may differ according to other exemplary embodiments, and that such variations are intended to be encompassed by the present disclosure.
It is important to note that the construction and arrangement of the various exemplary embodiments are illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter described herein. For example, elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes and omissions may also be made in the design, operating conditions and arrangement of the various exemplary embodiments without departing from the scope of the present invention. For example, the heat recovery heat exchangers may be further optimized.
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